Total synthesis of (+)-superstolide A.
A convergent and highly stereocontrolled total synthesis of the cytotoxic macrolide (+)-superstolide A is described. Key features of this synthesis include the use of bimetallic linchpin 36b for uniting the C(1)-C(15) (43) and the C(20)-C(27) (38) fragments of the natural product, a late-stage Suzuki macrocyclization of 49, and a highly diastereoselective transannular Diels-Alder reaction of macrocyclic octaene 4. In contrast, the intramolecular Diels-Alder reaction of pentaenal 5 provided the desired cycloadduct with lower stereoselectivity (6:1:1).
Tortosa
Mariola
M
Department of Chemistry, Scripps Florida, Jupiter, Florida 33458, USA.
Yakelis
Neal A
NA
Roush
William R
WR
D000438:Alcohols / Q000138:chemical synthesis; D000818:Animals; D003500:Cyclization; D003603:Cytotoxins / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D018942:Macrolides / Q000138:chemical synthesis*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D011161:Porifera / Q000737:chemistry; D013764:Tetrahydronaphthalenes / Q000138:chemical synthesis*
D000438:Alcohols; D003603:Cytotoxins; D007202:Indicators and Reagents; D018942:Macrolides; D013764:Tetrahydronaphthalenes; C091984:superstolide A